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Carbon Future https://doi.org/10.26599/CF.2024.9200008
Research Article | Open Access | Online first | Published: 04 February 2024

Identification of role of nitrogen dopants in nanocarbon catalysis

Show Author's Information Xuefei Zhang1,2,  Xinying Lin1,  Xiaoyan Huang1,  Yiquan Chen1,  Sen Lin1,  Xing Huang1,  Zailai Xie1( )
Key Laboratory of Advanced Carbon-Based Functional Materials (Fujian Province University), Fuzhou University, Fuzhou 350016, China
College of Chemical Engineering, Fuzhou University, Fuzhou 350016, China
Keywords:
heterogeneous catalysis, N-doped carbon, charge polarization, catalytic mechanism, active sites
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Zhang X, Lin X, Huang X, et al. Identification of role of nitrogen dopants in nanocarbon catalysis. Carbon Future, 2024, https://doi.org/10.26599/CF.2024.9200008
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Abstract Full text Electronic supplementary material About this article

The influence of nitrogen dopants on the catalytic activity of carbon-based materials has been studied extensively, but the exact role of nitrogen species in these materials remains unclear. A challenge in understanding the role of nitrogen is that most nitrogen-doped nanocarbon (NC) materials are dominated by uncontrollable surface functional groups, and changes in nitrogen species often lead to variations in oxygen functional groups, which makes the specific role of nitrogen difficult to isolate. To address this issue, we developed a series of NCs containing variable types and contents of nitrogen (approximately 5–30 at.%) and a constant oxygen content of approximately 4 at.%. Results show that the different types of nitrogen in the NCs, namely, graphitic nitrogen and pyridinic nitrogen, serve as electron-donating and -withdrawing modulators, respectively, and can tailor the oxidative dehydrogenation activity of the NCs. Additionally, graphitic nitrogen plays a role in mediating frustrated Lewis pairs consisting of pyridinic nitrogen and neighboring carbon atoms. These pairs are responsible for the activation of hydrogen–hydrogen bonds, which is the rate-determining step in nitrobenzene hydrogenation.


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About this article

Identification of role of nitrogen dopants in nanocarbon catalysis

Show Author's information Xuefei Zhang1,2, Xinying Lin1, Xiaoyan Huang1, Yiquan Chen1, Sen Lin1, Xing Huang1, Zailai Xie1( )
Key Laboratory of Advanced Carbon-Based Functional Materials (Fujian Province University), Fuzhou University, Fuzhou 350016, China
College of Chemical Engineering, Fuzhou University, Fuzhou 350016, China

Abstract

The influence of nitrogen dopants on the catalytic activity of carbon-based materials has been studied extensively, but the exact role of nitrogen species in these materials remains unclear. A challenge in understanding the role of nitrogen is that most nitrogen-doped nanocarbon (NC) materials are dominated by uncontrollable surface functional groups, and changes in nitrogen species often lead to variations in oxygen functional groups, which makes the specific role of nitrogen difficult to isolate. To address this issue, we developed a series of NCs containing variable types and contents of nitrogen (approximately 5–30 at.%) and a constant oxygen content of approximately 4 at.%. Results show that the different types of nitrogen in the NCs, namely, graphitic nitrogen and pyridinic nitrogen, serve as electron-donating and -withdrawing modulators, respectively, and can tailor the oxidative dehydrogenation activity of the NCs. Additionally, graphitic nitrogen plays a role in mediating frustrated Lewis pairs consisting of pyridinic nitrogen and neighboring carbon atoms. These pairs are responsible for the activation of hydrogen–hydrogen bonds, which is the rate-determining step in nitrobenzene hydrogenation.

Keywords: heterogeneous catalysis, N-doped carbon, charge polarization, catalytic mechanism, active sites

References(52)

[1]

Zhang, X. F.; Lu, Y. B.; Han, Y. Y.; Feng, R. P.; Xie, Z. L. Unravelling the role of boron dopant in borocarbonitirde catalytic dehydrogenation reaction. J. Energy Chem. 2023, 85, 137–143.
DOI Google Scholar
[2]

Zhang, X. F.; Dai, X. Y.; Wu, K. H.; Su, B. J.; Chen, J. M.; Qi, W.; Xie, Z. L. A generalized approach to adjust the catalytic activity of borocarbonitride for alkane oxidative dehydrogenation reactions. J. Catal. 2022, 405, 105–115.
DOI Google Scholar
[3]

Zhang, H. X.; Fan, W. W.; Xia, Q. H.; Yang, H. M. Protein-assisted synthesis of zeolite-supported pseudo-single-atom cobalt catalyst for nitrobenzene hydrogenation. Chem. Eng. J. 2023, 469, 143870.
DOI Google Scholar
[4]

Luo, Z. C.; Nie, R. F.; Nguyen, V. T.; Biswas, A.; Behera, R. K.; Wu, X.; Kobayashi, T.; Sadow, A.; Wang, B.; Huang, W. Y. et al. Transition metal-like carbocatalyst. Nat. Commun. 2020, 11, 4091.
DOI Google Scholar
[5]

Ortiz-Medina, J.; Wang, Z. P.; Cruz-Silva, R.; Morelos-Gomez, A.; Wang, F.; Yao, X. D.; Terrones, M.; Endo, M. Defect engineering and surface functionalization of nanocarbons for metal-free catalysis. Adv. Mater. 2019, 31, 1805717.
DOI Google Scholar
[6]

Yang, N. J.; Zhang, H. Nanocarbon chemistry. Small 2019, 15, 1905367.
DOI Google Scholar
[7]

Shi, L.; Qi, W.; Liu, W.; Yan, P. Q.; Li, F.; Sun, J. M.; Su, D. S. Carbon nitride modified nanocarbon materials as efficient non-metallic catalysts for alkane dehydrogenation. Catal. Today 2018, 301, 48–54.
DOI Google Scholar
[8]

Li, G. Z.; Zheng, S. Y.; Wang, L.; Zhang, X. W. Metal-free chemoselective hydrogenation of nitroarenes by N-doped carbon nanotubes via in situ polymerization of pyrrole. ACS Omega 2020, 5, 7519–7528.
DOI Google Scholar
[9]

Liu, W.; Wang, C.; Herold, F.; Etzold, B. J. M.; Su, D. S.; Qi, W. Oxidative dehydrogenation on nanocarbon: Effect of heteroatom doping. Appl. Catal. B:Environ. 2019, 258, 117982.
DOI Google Scholar
[10]

Liu, N.; Ding, L. Z.; Li, H. J.; Jia, M. J.; Zhang, W. X.; An, N. H.; Yuan, X. L. N-doped nanoporous carbon as efficient catalyst for nitrobenzene reduction in sulfide-containing aqueous solutions. J. Colloid Interface Sci. 2017, 490, 677–684.
DOI Google Scholar
[11]

Huang, X. X.; Wu, S. L.; Xiao, Z. C.; Kong, D. B.; Liang, T.; Li, X. L.; Luo, B.; Wang, B.; Zhi, L. J. Predicting the optimal chemical composition of functionalized carbon catalysts towards oxidative dehydrogenation of ethanol to acetaldehyde. Nano Today 2022, 44, 101508.
DOI Google Scholar
[12]

Hou, Y.; Xia, M.; Han, Y. Y.; Zhang, X. F.; Lu, Y. B.; Yang, Q. H.; Xie, Z. L. Folic Acid-Derived Low-dimensional carbons for efficient oxidative dehydrogenation of ethylbenzene. J. Colloid Interface Sci. 2023, 638, 291–299.
DOI Google Scholar
[13]

Zhang, Z.; Yu, L.; Tu, Y. C.; Chen, R. X.; Wu, L. H.; Zhu, J. F.; Deng, D. H. Unveiling the active site of metal-free nitrogen-doped carbon for electrocatalytic carbon dioxide reduction. Cell Rep. Phys. Sci. 2020, 1, 100145.
DOI Google Scholar
[14]

Lepre, E.; Rat, S.; Cavedon, C.; Seeberger, P. H.; Pieber, B.; Antonietti, M.; López-Salas N. Catalytic properties of high nitrogen content carbonaceous materials. Angew. Chem. , Int. Ed. 2023, 62, e202211663.
DOI Google Scholar
[15]

Otero, R.; Schöck, M.; Molina, L. M.; Lægsgaard, E.; Stensgaard, I.; Hammer, B.; Besenbacher, F. Guanine quartet networks stabilized by cooperative hydrogen bonds. Angew. Chem. , Int. Ed. 2005, 44, 2270–2275.
DOI Google Scholar
[16]

Peters, G. M.; Davis, J. T. Supramolecular gels made from nucleobase, nucleoside and nucleotide analogs. Chem. Soc. Rev. 2016, 45, 3188–3206.
DOI Google Scholar
[17]

Wagner, A.; Upcher, A.; Maria, R.; Magnesen, T.; Zelinger, E.; Raposo, G.; Palmer, B. A. Macromolecular sheets direct the morphology and orientation of plate-like biogenic guanine crystals. Nat. Commun. 2023, 14, 589.
DOI Google Scholar
[18]

Huang, B. B.; Liu, Y. C.; Xie, Z. L. Two dimensional nanocarbons from biomass and biological molecules: Synthetic strategies and energy related applications. J. Energy Chem. 2021, 54, 795–814.
DOI Google Scholar
[19]

Huang, B. B.; Liu, Y. C.; Guo, Q.; Fang, Y. X.; Titirici, M. M.; Wang, X. C.; Xie, Z. L. Porous carbon nanosheets from biological nucleobase precursor as efficient pH-independent oxygen reduction electrocatalyst. Carbon 2020, 156, 179–186.
DOI Google Scholar
[20]

Kossmann, J.; Heil, T.; Antonietti, M.; López-Salas, N. Guanine-derived porous carbonaceous materials: Towards C1N1. ChemSusChem 2020, 13, 6643–6650.
DOI Google Scholar
[21]

Stefan, L.; Monchaud, D. Applications of guanine quartets in nanotechnology and chemical biology. Nat. Rev. Chem. 2019, 3, 650–668.
DOI Google Scholar
[22]

Herold, F.; Prosch, S.; Oefner, N.; Brunnengräber, K.; Leubner, O.; Hermans, Y.; Hofmann, K.; Drochner, A.; Hofmann, J. P.; Qi, W. et al. Nanoscale hybrid amorphous/graphitic carbon as key towards next-generation carbon-based oxidative dehydrogenation catalysts. Angew. Chem. , Int. Ed. 2021, 60, 5898–5906.
DOI Google Scholar
[23]

Um, J.; Yoon, S. U.; Kim, H.; Youn, B. S.; Jin, H. J.; Lim, H. K.; Yun, Y. S. High-performance solid-solution potassium-ion intercalation mechanism of multilayered turbostratic graphene nanosheets. J. Energy Chem. 2022, 67, 814–823.
DOI Google Scholar
[24]

Zhi, C. Y.; Bando, Y.; Tang, C. C.; Honda, S.; Sato, K.; Kuwahara, H.; Golberg, D. Covalent functionalization: Towards soluble multiwalled boron nitride nanotubes. Angew. Chem. , Int. Ed. 2005, 44, 7932–7935.
DOI Google Scholar
[25]

Lv, C. D.; Qian, Y. M.; Yan, C. S.; Ding, Y.; Liu, Y. Y.; Chen, G.; Yu, G. H. Defect engineering metal-free polymeric carbon nitride electrocatalyst for effective nitrogen fixation under ambient conditions. Angew. Chem. , Int. Ed. 2018, 57, 10246–10250.
DOI Google Scholar
[26]

Al-Zahrani, A. A.; Pasupulety, N.; Daous, M. A.; Driss, H.; Ali, A. M.; Zaman, S. F.; Petrov, L. A. Ethyl benzene oxidative dehydrogenation to styrene on Al-B and Al-B-Sb catalysts. Appl. Catal. A:Gen. 2018, 552, 49–57.
DOI Google Scholar
[27]

Xu, J.; Xue, B.; Liu, Y. M.; Li, Y. X.; Cao, Y.; Fan, K. N. Mesostructured Ni-doped ceria as an efficient catalyst for styrene synthesis by oxidative dehydrogenation of ethylbenzene. Appl. Catal. A:Gen. 2011, 405, 142–148.
DOI Google Scholar
[28]

Rennard, R. J. Jr.; Innes, R. A.; Swift, H. E. Oxidation over MgCrFeO4 and ZnCrFeO4 catalysts. J. Catal. 1973, 30, 128–138.
DOI Google Scholar
[29]

Emig, G.; Hofmann, H. Action of zirconium phosphate as a catalyst for the oxydehydrogenation of ethylbenzene to styrene. J. Catal. 1983, 84, 15–26.
DOI Google Scholar
[30]

Zhang, J.; Su, D. S.; Zhang, A. H.; Wang, D.; Schlögl, R.; Hébert, C. Nanocarbon as robust catalyst: Mechanistic insight into carbon-mediated catalysis. Angew. Chem. , Int. Ed. 2007, 46, 7319–7323.
DOI Google Scholar
[31]

Shan, J. X.; Sun, X. Q.; Zheng, S. Y.; Wang, T. D.; Zhang, X. W.; Li, G. Z. Graphitic N-dominated nitrogen-doped carbon nanotubes as efficient metal-free catalysts for hydrogenation of nitroarenes. Carbon 2019, 146, 60–69.
DOI Google Scholar
[32]

Xiong, W.; Wang, Z. N.; He, S. L.; Hao, F.; Yang, Y. Z.; Lv, Y.; Zhang, W. B.; Liu, P. L.; Luo, H. Nitrogen-doped carbon nanotubes as a highly active metal-free catalyst for nitrobenzene hydrogenation. Appl. Catal. B:Environ. 2020, 260, 118105.
DOI Google Scholar
[33]

Xu, F.; Zhai, Y. X.; Zhang, E.; Liu, Q. H.; Jiang, G. S.; Xu, X. S.; Qiu, Y. Q.; Liu, X. M.; Wang, H. Q.; Kaskel, S. Ultrastable surface-dominated pseudocapacitive potassium storage enabled by edge-enriched n-doped porous carbon nanosheets. Angew. Chem. , Int. Ed. 2020, 59, 19460–19467.
DOI Google Scholar
[34]

Zhang, X. F.; Yan, P. Q.; Xu, J. K.; Li, F.; Herold, F.; Etzold, B. J. M.; Wang, P.; Su, D. S.; Lin, S.; Qi, W. et al. Methanol conversion on borocarbonitride catalysts: Identification and quantification of active sites. Sci. Adv. 2020, 6, eaba5778.
DOI Google Scholar
[35]

Ou, H. H.; Lin, L. H.; Zheng, Y.; Yang, P. J.; Fang, Y. X.; Wang, X. C. Tri-s-triazine-based crystalline carbon nitride nanosheets for an improved hydrogen evolution. Adv. Mater. 2017, 29, 1700008.
DOI Google Scholar
[36]

Qi, W.; Liu, W.; Guo, X. L.; Schlögl, R.; Su, D. S. Oxidative dehydrogenation on nanocarbon: Intrinsic catalytic activity and structure-function relationships. Angew. Chem. , Int. Ed. 2015, 54, 13682–13685.
DOI Google Scholar
[37]

Frank, B.; Zhang, J.; Blume, R.; Schlögl, R.; Su, D. S. Heteroatoms increase the selectivity in oxidative dehydrogenation reactions on nanocarbons. Angew. Chem. , Int. Ed. 2009, 48, 6913–6917.
DOI Google Scholar
[38]

Chen, D. J.; Wang, Y. T.; Klankermayer, J. Enantioselective hydrogenation with chiral frustrated Lewis pairs. Angew. Chem. , Int. Ed. 2010, 49, 9475–9478.
DOI Google Scholar
[39]

Stephan, D. W. Frustrated Lewis pairs. J. Am. Chem. Soc. 2015, 137, 10018–10032.
DOI Google Scholar
[40]

Liu, L.; Cao, L. L.; Shao, Y.; Ménard, G.; Stephan, D. W. A radical mechanism for frustrated Lewis pair reactivity. Chem 2017, 3, 259–267.
DOI Google Scholar
[41]

Wan, Q.; Chen, Y.; Zhou, S. L.; Lin, J.; Lin, S. Selective hydrogenation of acetylene to ethylene on anatase TiO2 through first-principles studies. J. Mater. Chem. A 2021, 9, 14064–14073.
DOI Google Scholar
[42]

Huang, X. Y.; Zeng, X. H.; Zhang, X. F.; Xie, Z. L. Carbon-based frustrated Lewis pairs mediate hydrogenation. Phys. Chem. Chem. Phys. 2022, 24, 28895–28902.
DOI Google Scholar
[43]

Liao, C. J.; Liu, B.; Chi, Q.; Zhang, Z. H. Nitrogen-doped carbon materials for the metal-free reduction of nitro compounds. ACS Appl. Mater. Interfaces 2018, 10, 44421–44429.
DOI Google Scholar
[44]

Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15–50.
DOI Google Scholar
[45]

Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169–11186.
DOI Google Scholar
[46]

Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758–1775.
DOI Google Scholar
[47]

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953–17979.
DOI Google Scholar
[48]

Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132, 154104.
DOI Google Scholar
[49]

Henkelman, G.; Uberuaga, B. P.; Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 2000, 113, 9901–9904.
DOI Google Scholar
[50]
Henkelman, G.; Jónsson, H. A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives. J. Chem. Phys. 1999, 111, 7010–7022.
DOI
[51]

Olsen, R. A.; Kroes, G. J.; Henkelman, G.; Arnaldsson, A.; Jónsson, H. Comparison of methods for finding saddle points without knowledge of the final states. J. Chem. Phys. 2004, 121, 9776–9792.
DOI Google Scholar
[52]

Heyden, A.; Bell, A. T.; Keil, F. J. Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method. J. Chem. Phys. 2005, 123, 224101.
DOI Google Scholar
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Received: 14 November 2023
Revised: 14 December 2023
Accepted: 30 December 2023
Published: 04 February 2024

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© The Author(s) 2024.

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Acknowledgements

The authors greatly acknowledge the financial support from the National Natural Science Foundation of China (22072018 and 22372039) and the Natural Science Foundation of Fujian Province of China (2021J06010).

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